EP3235801B1

EP3235801B1 - Carboxylic acid ester production method

Info

Publication number: EP3235801B1
Application number: EP15869904.1A
Authority: EP
Inventors: Akihiro Goto; Yoshihiro Kamon; Hiroyuki Mori
Original assignee: Mitsubishi Chemical Corp
Current assignee: Mitsubishi Chemical Corp
Priority date: 2014-12-18
Filing date: 2015-12-11
Publication date: 2019-02-20
Anticipated expiration: 2035-12-11
Also published as: JPWO2016098699A1; KR102478883B1; WO2016098699A1; KR20170094118A; US10421705B2; CN107074719A; CN107074719B; US20180354885A1; EP3235801A4; JP6597312B2; EP3235801A1

Description

Technical Field

The present invention relates to a method for producing a carboxylic acid ester.

Background Art

Carboxylic acid esters are broadly used as solvents as well as raw materials for fragrances, resins, coatings, adhesives and the like. In a known carboxylic acid ester production method, di-t-butyl dicarbonate, a carboxylic acid and an alcohol are reacted to produce the corresponding carboxylic acid ester.
Non-Patent Literature 1 describes a method for producing a carboxylic acid ester by reacting di-t-butyl dicarbonate, a carboxylic acid and an alcohol in the presence of magnesium chloride.
Non-Patent Literature 2 describes a method for producing a carboxylic acid ester by reacting di-t-butyl dicarbonate, a carboxylic acid and an alcohol in the presence of an amine.

PRIOR ART LITERATURE

NON-PATENT LITERATURE

Non-Patent Literature 1: Synthesis 2007, 3489
Non-Patent Literature 2: Advanced Synthesis Catalysis, 2008, 350, 1891

SUMMARY OF THE INVENTION

PROBLEMS TO BE SOLVED BY THE INVENTION

However, in the carboxylic acid ester production method described in Non-Patent Literature 1, the amount of alcohol exceeds the theoretically estimated amount, thus making the method economically unfavorable. In addition, since it is necessary to use a catalyst at 0.1 molar equivalent to the carboxylic acid, the method is inefficient. The inventors of the present invention have studied the method and found that when the catalyst amount is reduced for reacting di-t-butyl dicarbonate, a carboxylic acid and an alcohol, reaction does not progress, or even if reaction progresses, the yield of the produced carboxylic acid ester is low. Also, the inventors have found that the substrate generality is narrow since reaction is less likely to progress when phenyl (meth)acrylate is synthesized by a known method.
In the carboxylic acid ester production method described in Non-Patent Literature 2, since it is necessary to use triethyl amine as an additive at 2 molar equivalent to the carboxylic acid, the method is inefficient. In addition, to remove the triethylamine after the reaction is completed, it is necessary to prepare an organic solvent, acidic aqueous solution and basic aqueous solution, thus resulting in a large amount of waste and making the method not only less cost-effective but also environmentally problematic. In addition, the method requires adding the alcohol and di-t-butyl dicarbonate to a -20°C reaction mixture separately prepared and then heating the mixture to room temperature. Thus, the reaction process is complicated, and reaction efficiency is low. The inventors of the present invention have studied the method and found that when di-t-butyl dicarbonate, a carboxylic acid and an alcohol are reacted by using a reduced amount of catalyst and additive, reaction does not progress, and even if reaction progresses, the yield of the produced carboxylic acid ester is low.
Accordingly, the objective of the present invention is to provide a method for producing corresponding carboxylic acid esters from various carboxylic acids at high yield under conditions such as a simplified reaction process, a smaller amount of catalyst, and a theoretically estimated amount of substrate.

SOLUTIONS TO THE PROBLEMS

The inventors of the present invention have intensively studied the problems of conventional technology and found that the above objective is achieved when a specific catalyst is used for the reaction. Accordingly, the present invention has been completed.
Namely, an aspect of the present invention is a method for producing a carboxylic acid ester as defined by claim 1 by reacting a compound represented by formula (I) below, a carboxylic acid and an alcohol in the presence of at least one type of magnesium compound and at least one type of alkali metal compound. In formula (I), R¹ and R² each indicate a C1∼C20 hydrocarbon group.

EFFECTS OF THE INVENTION

In the carboxylic acid ester production method related to the present invention, a carboxylic acid ester is obtained at high yield even when a substrate is set at a theoretically estimated amount. Accordingly, the carboxylic acid ester is produced more efficiently and more cost-effectively than by conventional methods.
In the carboxylic acid ester production method related to the present invention, a carboxylic acid ester is obtained at high yield even when a smaller amount of catalyst is used. Accordingly, the carboxylic acid ester is produced more efficiently and more cost-effectively than by conventional methods and with less environmental load.
In the carboxylic acid ester production method related to the present invention, the raw materials are supplied into a reactor all at once. Accordingly, the carboxylic acid ester is produced more efficiently in a more simplified process than by conventional methods.
In the carboxylic acid ester production method related to the present invention, various types of carboxylic acid and various types of alcohol can be used as raw materials. Thus, the substrate generality is significantly broader than that in conventional technology.

MODE TO CARRY OUT THE INVENTION

In the present application, acrylic acid and methacrylic acid are collectively referred to as (meth)acrylic acid, and acrylic acid esters and methacrylic acid esters are also collectively referred to as (meth)acrylic acid esters.

[Compound Represented by Formula (I)]

In the carboxylic acid ester production method related to the present invention, a compound represented by formula (I) is used as raw material. During the reaction, a compound represented by formula (I) generates an intermediate that contains a component derived from the compound. However, the resulting carboxylic acid ester does not contain such a component that is derived from the compound.
In formula (I), R¹ and R² each independently indicate a C1∼C20 hydrocarbon group. As long as R¹ and R² are each a hydrocarbon group, its type and structure are not particularly limited. The hydrocarbon group may be in a linear, branched-chain or ring structure, or may have an unsaturated or ether bond. R¹ and R² may be bonded to form a ring structure.
Examples of a hydrocarbon group are alkyl group, alkenyl group, alkynyl group and aryl group. The number of carbon atoms in such a hydrocarbon group is preferred to be 1∼20, more preferably 2∼10, even more preferably 3∼7, since it is easier to obtain a compound represented by formula (I) having such a group.
Particular examples of a hydrocarbon group are an allyl group, t-butyl group, t-amyl group, benzyl group and the like. Also, examples of a compound represented by formula (I) are diallyl dicarbonate, di-t-butyl dicarbonate, di-t-amyl dicarbonate, dibenzyl dicarbonate, and the like. Among them, it is preferred to be di-t-butyl dicarbonate where R¹ and R² are each a t-butyl group, since using such a compound makes it easier to efficiently synthesize a carboxylic acid ester.
As for a compound represented by formula (I), it is an option to use a commercially available compound or a compound produced by a known method or the like. In addition, compounds represented by formula (I) may be used alone or in combination thereof.

[Carboxylic Acid]

In the method for producing a carboxylic acid ester related to the present invention, the type and structure are not limited specifically for a carboxylic acid to be used as raw material. For example, a carboxylic acid is denoted as "R³-COOH," where R³ is preferred to be a C1∼C30 hydrocarbon group that may have a substituent. The hydrocarbon group may be in a linear, branched-chain, or ring structure that may contain an unsaturated or ether bond. In the present application, "may have a substituent" means containing at least one substituent of any type, for example, the following bond, group or atom: ester bond, amide bond, ether bond, sulfide bond, disulfide bond, urethane bond, nitro group, cyano group, ketone group, formyl group, acetal group, thioacetal group, sulfonyl group, halogen, silicon, phosphorous and the like.
As for the hydrocarbon group in a carboxylic acid, it may be, for example, an alkyl, alkenyl, alkynyl or aryl group. The number of carbon atoms in such a hydrocarbon group is preferred to be 1∼30, more preferably 2∼20, considering the ease of obtaining such a carboxylic acid.
More particular examples of a hydrocarbon group are a vinyl group, isopropenyl group, t-butyl group, hexyl group, cyclohexyl group, phenyl group and the like. Specific examples of a carboxylic acid are (meth)acrylic acid, pivalic acid, heptanoic acid, cyclohexanecarboxylic acid, benzoic acid, monomethyl adipate, 6-chlorohexanoic acid, and the like. Among them, R³ is more preferred to be a vinyl or isopropenyl group. It is especially preferred to use (meth)acrylic acid due to the broad application range of carboxylic acid esters.
As for a carboxylic acid, it is an option to use a commercially available type or a type produced by a known method or the like. In addition, carboxylic acids may be used alone or in combination thereof. Also, oligo- and poly-carboxylic acids may be used.
In the carboxylic acid ester production method related to the present invention, the amount of a carboxylic acid to be used is preferred to be in a range of 0.1∼10 mol, more preferably 0.2∼5 mol, even more preferably 0.5∼2 mol, relative to 1 mol of the compound represented by formula (I) above. By setting the amount of a carboxylic acid to be at least 0.1 mol relative to 1 mol of the compound represented by formula (I), the yield of a resulting carboxylic acid ester is enhanced. By setting the amount of carboxylic acid to be no greater than 10 mol relative to 1 mol of the compound represented by formula (I), load on the postreaction treatment is alleviated, thus achieving more cost effective production.

[Alcohol]

In the method for producing carboxylic acid ester related to the present invention, the type and structure of an alcohol as raw material for the carboxylic acid ester are not particularly limited. For example, alcohol is denoted as "R⁴-OH," where R⁴ is preferred to be a C1∼C30 hydrocarbon group that may have a substituent. The hydrocarbon group may be in a linear, branched-chain, or ring structure that may contain an unsaturated bond. "May have a substituent" means containing at least one substituent of any type, for example, the following bond, group or atom: ester bond, amide bond, ether bond, sulfide bond, disulfide bond, urethane bond, nitro group, cyano group, ketone group, formyl group, acetal group, thioacetal group, sulfonyl group, halogen, silicon, phosphorous and the like.
As for the hydrocarbon group contained in an alcohol, it may be, for example, an alkyl, alkenyl, alkynyl or aryl group. The number of carbon atoms in such a hydrocarbon group is preferred to be 1∼30, more preferably 2∼20, considering the ease of obtaining such an alcohol. Among them, the hydrocarbon group is preferred to be an aryl group. It is preferred to use aromatic alcohol capable of producing aromatic-alcohol-derived carboxylic acid esters, which conventionally have been difficult to synthesize at high yield. Specific examples are phenol, phenylphenol, naphthol, and the like.
As for an alcohol, it is an option to use a commercially available type or a type produced by a known method or the like. In addition, alcohols may be used alone or in combination thereof. Also, oligo- and poly-hydric alcohols may be used.
The amount of an alcohol to be used is preferred to be in a range of 0.1∼10 mol, more preferably 0.2∼5 mol, even more preferably 0.5∼2 mol, relative to 1 mol of the compound represented by formula (I) above. By setting the amount of an alcohol to be at least 0.1 mol relative to 1 mol of the compound represented by formula (I), the yield of a resulting carboxylic acid ester is enhanced. By setting the amount of alcohol to be no greater than 10 mol relative to 1 mol of the compound represented by formula (I), load on the postreaction treatment is alleviated, thus making production more cost-effective.
The amount of an alcohol to be used is preferred to be in a range of 0.1∼10 mol, more preferably 0.2∼5 mol, even more preferably 0.5∼2 mol, relative to 1 mol of the carboxylic acid. By setting the amount of an alcohol to be at least 0.1 mol relative to 1 mol of the carboxylic acid, the yield of a resulting carboxylic acid ester is enhanced. By setting the amount of alcohol to be no greater than 10 mol relative to 1 mol of the carboxylic acid, load on the postreaction treatment is alleviated, thus making production more cost-effective.

[Catalyst for Producing Carboxylic Acid Ester]

The catalyst used in the method for producing a carboxylic acid ester related to the present invention is a magnesium compound and an alkali metal compound. Since the solubility of a catalyst depends on the ligand of the catalyst, the catalyst may be used either as a homogeneous or heterogeneous catalyst.
In the method for producing a carboxylic acid ester related to the present invention, a compound represented by formula (I), a carboxylic acid and an alcohol are reacted in the presence of a catalyst. "In the presence of a catalyst" means a catalyst is present at least in part of the reaction process. It is not necessary for the catalyst to be present in the entire reaction process. In the method for producing a carboxylic acid ester related to the present invention, as long as a catalyst is added to a reaction system, the requirement of "in the presence of a catalyst" is satisfied. For example, after a catalyst is added into the reaction system, even if some change occurs in the catalyst during the reaction process, the requirement of "in the presence of a catalyst" is satisfied.

[Magnesium Compound]

The magnesium compound is a salt with inorganic acids such as magnesium oxide, magnesium hydroxide, magnesium carbonate, magnesium bicarbonate, magnesium silicate, magnesium sulfate, ammonium magnesium sulfate, magnesium nitrate, magnesium phosphate, magnesium hydrogen phosphate, ammonium magnesium phosphate, magnesium borate, a magnesium salt of halogen acids, a magnesium perhalogenate, and a magnesium salt of hydrohalic acids; a salt with organic acids such as magnesium carboxylate, magnesium peroxycarboxylate, and magnesium sulfonate; a complex salt such as magnesium acetylacetonate, magnesium hexafluoroacetylacetonate, magnesium porphyrin, magnesium phthalocyanine, and magnesium cyclopentadienyl. These magnesium salts may be any hydrate or anhydride. Among them, magnesium oxide, magnesium hydroxide, magnesium carbonate, magnesium sulfate, ammonium magnesium sulfate, magnesium nitrate, magnesium salts of hydrohalic acids, magnesium carboxylate, and magnesium complex are preferred. More specific examples of a magnesium compound are magnesium oxide, magnesium hydroxide, magnesium carbonate hydroxide (also known as basic magnesium carbonate), magnesium sulfate, ammonium magnesium sulfate, magnesium nitrate, magnesium chloride, magnesium bromide, magnesium acetate, magnesium benzoate, magnesium (meth)acrylate, magnesium acetylacetonate, and the like.
As for a magnesium compound, it is an option to use a commercially available type or a type produced by a known method or the like. In addition, such compounds may be used alone or in combination thereof.
The amount of a magnesium compound to be used is in a range of 0.001∼1000 mol%, preferably 0.005∼500 mol%, relative to the compound represented by formula (I). By setting the amount of a magnesium compound to be at least 0.001 mol% of the compound represented by formula (I), the yield of a resulting carboxylic acid ester is enhanced. The amount is preferred to be no greater than 1000 mol% of the compound represented by formula (I), because any significant increase in the effect is unlikely if it is set beyond 1000 mol%.
The amount of a magnesium compound is preferred to be in a range of 0.001∼1000 mol%, more preferably 0.005∼500 mol%, even more preferably 0.01∼250 mol%, relative to the amount of alcohol. By setting the amount of a magnesium compound to be at least 0.001 mol% of the alcohol, the yield of a resulting carboxylic acid ester is enhanced. The amount is preferred to be no greater than 1000 mol% of the alcohol, because any significant increase in the effect is unlikely if it is set beyond 1000 mol%.

[Alkali Metal Compound]

The alkali metal compound is a salt with inorganic acids such as alkali metal hydrides, oxides, hydroxides, carbonates, bicarbonates, sulfates, nitrates, phosphates, borates, a salt of halogen acids, perhalogenates, a salt of hydrohalic acids, and thiocyanates; a salt with organic acids such as alkali metal alkoxides, carboxylates, and sulfonates; a salt with organic bases such as alkali metal amides and sulfoamides; a complex salt such as alkali metal acetylacetonates, hexafluoroacetylacetonates, porphyrins, phthalocyanates, and cyclopentadienates. These alkali metal salts may be any hydrate or anhydride. Among them, alkali metal oxides, hydroxides, carbonates, dicarbonates, salts of hydrohalic acids, carboxylates, amides and complexes are preferred.
The metal in an alkali metal compound is not limited specifically. Among the metals that belong to alkali metals, lithium, sodium, potassium, rubidium and cesium are preferred, more preferably lithium, because of high catalytic activity. Specific examples of a lithium compound are lithium oxide, lithium hydroxide, lithium carbonate, lithium fluoride, lithium chloride, lithium bromide, lithium acetate, lithium benzoate, lithium (meth)acrylate, lithium amide, lithium triflimide, lithium acetylacetonate, and the like.
Alkali metal compounds may be obtained commercially, or produced by a known method or the like. They may be used alone or in combination thereof.
The amount of an alkali metal compound to be used is in a range of 0.001∼1000 mol%, preferably 0.005∼500 mol%, relative to the compound represented by formula (I). By setting the amount of an alkali metal compound to be at least 0.001 mol% of the compound represented by formula (I), the yield of a resulting carboxylic acid ester is enhanced. The amount is preferred to be no greater than 1000 mol% of the compound represented by formula (I), because any significant increase in the effect is unlikely if it is set beyond 1000 mol%.
The amount of an alkali metal compound is preferred to be in a range of 0.001∼1000 mol%, more preferably 0.005∼500 mol%, even more preferably 0.01∼250 mol% relative to the amount of alcohol. By setting the amount of an alkali metal compound to be at least 0.001 mol% of the alcohol, the yield of a resulting carboxylic acid ester is enhanced. The amount is preferred to be no greater than 1000 mol% of the alcohol, because any significant increase in the effect is unlikely if it is set beyond 1000 mol%.

[Reaction Conditions for Producing Carboxylic Acid Ester]

The reaction conditions in the method for producing carboxylic acid ester related to the present invention are not particularly limited, and may be modified appropriately during the reaction process.
The reactor is not limited to any particular type. The reaction temperature is not limited specifically either, and may be set in a range of -20∼180°C, preferably 0∼100°C. By setting the reaction temperature to be at least -20°C, reaction progresses efficiently. When the reaction temperature is set at 180°C or lower, the amount of byproduct is controlled and the coloring of the reaction mixture is suppressed.
The reaction time is not limited specifically; for example, it may be set for 0.5∼72 hours, preferably 2∼48 hours. When the reaction time is set to be at least 0.5 hours, reaction will progress sufficiently. The reaction time is set to be 72 hours or shorter, because any duration longer than 72 hours does not result in any significant increase in the effect.
No specific limitation is set on reaction ambience or reaction pressure.
The method for producing a carboxylic acid ester related to the present invention does not require any solvent. However, a solvent may be used depending on the situations such as when the viscosity of the reaction mixture is high. The type of solvent is not limited specifically; for example, a C1∼C25 organic compound may be used by selecting appropriately according to reaction conditions. Examples of a solvent are tetrahydrofuran and the like. Solvents may be used alone or in combination thereof. The amount of solvent is not limited particularly, and may be determined appropriately.
The raw material (compound represented by formula (I), carboxylic acid and alcohol), catalyst, solvent and the like if applicable, to be used for reaction, may be introduced into a reactor by any method; for example, all of the material may be introduced all at once, or part or all of the material may be introduced intermittently or continuously. Alternatively, a combination of those methods may be employed.

[Carboxylic Acid Ester]

The product obtained by the method for producing a carboxylic acid ester related to the present invention is denoted, for example, as "R³COOR⁴." R³ and R⁴ are those shown above in the descriptions of carboxylic acids and alcohols.
When a carboxylic acid used in the production method related to the present invention is (meth)acrylic acid, a (meth)acrylic acid ester is produced. Since (meth)acrylic acid and (meth)acrylic acid ester tend to polymerize, a polymerization inhibitor may be added in advance so as to prevent their polymerization. A polymerization inhibitor may be added at any time, but is preferred to be added at the start of reaction, since it is easier to carry out the reaction.
The type of polymerization inhibitor is not particularly limited; for example, it may be a known polymerization inhibitor such as 2,2,6,6-tetramethylpiperidine 1-oxyl free radical or the like. The inhibitors may be used alone or in combination thereof. The amount of polymerization inhibitor is preferred to be in a range of 0.001∼0.5 parts by mass, more preferably 0.01∼0.1 parts by mass, relative to 100 parts by mass of (meth)acrylic acid or (meth)acrylic acid ester. In addition, reaction may be carried out in a flow of an oxygen-containing gas such as air. The flow rate of gas may be determined according to reaction conditions or the like.
The carboxylic acid ester obtained by the method for producing a carboxylic acid ester related to the present invention may be used as is for the following reaction, or purified if necessary. Conditions for purifying the ester are not limited specifically, and may be modified appropriately during the reaction process or at the time of reaction completion. For example, after the reaction is completed, a carboxylic acid ester may be purified from the reaction mixture by vacuum distillation, chromatography, recrystallization or the like. Those methods may be employed alone or in combination thereof.
In the method for producing a carboxylic acid ester related to the present invention, the storage container for the obtained carboxylic acid ester is not particularly limited; for example, a glass, resin or metallic container may be used.

EXAMPLES

In the following, the present invention is described in detail by referring to examples. However, the present invention is not limited to those examples, and any modification is possible unless it deviates from the gist of the present invention.
The di-t-butyl dicarbonate used in the examples and comparative examples below is a compound with a purity of 98 mass% made by Tokyo Chemical Industry Co., Ltd., and R¹ and R² in formula (I) are C(CH₃)₃. In addition, tetrahydrofuran (hereinafter abbreviated as "THF") is a special grade (moisture rate of 0.05% or less) made by Kanto Chemical Co., Inc. The method for determining the yield of each product is as follows.
After the reaction was completed, a standard substance (anisole or 1,1,2,2-tetrachloroethane) was added to the reaction mixture. Then, the mixture was dissolved in deuterated chloroform (CDCl₃) and was analyzed by ¹H-NMR (270 MHz). By converting from the values obtained from integration of the signal intensities on the spectrum, the amount (mmol) of the produced carboxylic acid ester was determined. Next, the yield of the carboxylic acid ester was calculated by formula (1) (when the obtained yield is less than 1%, it will be denoted as zero).
$Yield of carboxylic acid ester (%) = (P_{1} / R_{1}) \times 100$

P₁=the amount of produced carboxylic acid ester (mmol)
R₁=the amount of alcohol used in the reaction (mmol)

Also, the amount (mol%) of each magnesium compound and alkali metal compound used as the catalyst was calculated by formula (2).
$The amount of catalyst (mol %) = (C_{1} / R_{1}) \times 100$

C₁=the amount of catalyst used in the reaction (mmol)
R₁=the amount of alcohol used in the reaction (mmol)

[Example 1]

In a 100 mL capacity eggplant-shaped flask, 10.000 grams (106.26 mmol) of phenol, 9.148 grams (106.26 mmol) of methacrylic acid, 23.664 grams (106.26 mmol) of di-t-butyl dicarbonate, 0.018 grams (0.43 mmol, 0.4 mol%) of lithium hydroxide monohydrate, and 0.024 grams (0.11 mmol, 0.1 mol%) of magnesium acetylacetonate were added successively. Then reaction was carried out at 25 °C while the mixture was stirred. Accordingly, phenyl methacrylate was produced. The reaction result obtained 5 hours after the start of reaction is shown in Table 1.

[Examples 2∼14]

In each of the examples, phenyl methacrylate was produced by conducting the same procedure as in Example 1 except that lithium hydroxide monohydrate as the catalyst was replaced with a type of alkali metal compound (0.4 mol%) shown in Table 1. The reaction result obtained 5 hours after the start of reaction in each example is shown in Table 1.

[Comparative Example 1]

Phenyl methacrylate was produced by carrying out the same procedure as in Example 1 except that lithium hydroxide monohydrate was not added. The reaction result obtained 5 hours after the start of reaction is shown in Table 1.

[Comparative Example 2]

The comparative example was conducted in an attempt to produce phenyl methacrylate by carrying out the same procedure as in Example 1 except that magnesium acetylacetonate was not added. The reaction result obtained 5 hours after the start of reaction is shown in Table 1.

[Comparative Example 3]

The comparative example was conducted in an attempt to produce phenyl methacrylate by carrying out the same procedure as in Comparative Example 2 except that the amount of lithium hydroxide monohydrate was changed to 2.0 mol%. The reaction result obtained 24 hours after the start of reaction is shown in Table 1.

[Comparative Examples 4∼10]

Each comparative example was conducted in an attempt to produce phenyl methacrylate by the same procedure as in Comparative Example 2 except that lithium hydroxide monohydrate was replaced with a type and amount of alkali metal compound (1.0 mol% or 2.0 mol%) specified in Table 1. The reaction result of each comparative example obtained 24 hours after the start of reaction is shown in Table 1.

Table 1

	magnesium compound	added amount (mol%)	alkali metal compound	added amount (mol%)	reaction time (hr.)	yield of phenyl methacrylate (%)
Example 1	magnesium acetylacetonate	0.1	lithium hydroxide monohydrate	0.4	5	82
Example 2	magnesium acetylacetonate	0.1	cesium hydroxide monohydrate	0.4	5	56
Example 3	magnesium acetylacetonate	0.1	lithium carbonate	0.4	5	78
Example 4	magnesium acetylacetonate	0.1	sodium carbonate	0.4	5	72
Example 5	magnesium acetylacetonate	0.1	potassium carbonate	0.4	5	68
Example 6	magnesium acetylacetonate	0.1	rubidium carbonate	0.4	5	53
Example 7	magnesium acetylacetonate	0.1	cesium carbonate	0.4	5	42
Example 8	magnesium acetylacetonate	0.1	lithium oxide	0.4	5	73
Example 9	magnesium acetylacetonate	0.1	lithium acetylacetonate	0.4	5	67
Example 10	magnesium acetylacetonate	0.1	lithium fluoride	0.4	5	77
Example 11	magnesium acetylacetonate	0.1	lithium chloride	0.4	5	82
Example 12	magnesium acetylacetonate	0.1	lithium bromide	0.4	5	86
Example 13	magnesium acetylacetonate	0.1	lithium amide	0.4	5	82
Example 14	magnesium acetylacetonate	0.1	lithium triflimide	0.4	5	71
Comp. Example 1	magnesium acetylacetonate	0.1	-	-	5	19
Comp. Example 2	-	-	lithium hydroxide monohydrate	0.4	5	0
Comp. Example 3	-	-	lithium hydroxide monohydrate	2.0	24	0
Comp. Example 4	-	-	cesium hydroxide monohydrate	2.0	24	0
Comp. Example 5	-	-	lithium carbonate	2.0	24	0
Com p. Example 6	-	-	sodium carbonate	2.0	24	0
Com p. Example 7	-	-	potassium carbonate	2.0	24	0
Com p. Example 8	-	-	rubidium carbonate	2.0	24	0
Com p. Example 9	-	-	cesium carbonate	2.0	24	0
Comp. Example 10	-	-	lithium bromide	1.0	24	0

[Examples 15∼19]

In each example, phenyl methacrylate was produced by carrying out the same procedure as in Example 1 except that the amount of lithium hydroxide monohydrate (0.1 mol%∼2.0 mol%) specified in Table 2 was used. The reaction result of each example obtained 5 hours or 24 hours after the start of reaction is shown in Table 2.

Table 2

	magnesium compound	added amount (mol%)	alkali metal compound	added amount (mol%)	reaction time (hr.)	yield of phenyl methacrylate (%)
Example 15	magnesium acetylacetonate	0.1	lithium hydroxide monohydrate	0.1	5	90
Example 15	magnesium acetylacetonate	0.1	lithium hydroxide monohydrate	0.1	24	94
Example 16	magnesium acetylacetonate	0.1	lithium hydroxide monohydrate	0.2	5	86
Example 16	magnesium acetylacetonate	0.1	lithium hydroxide monohydrate	0.2	24	95
Example 17	magnesium acetylacetonate	0.1	lithium hydroxide monohydrate	0.4	5	82
Example 17	magnesium acetylacetonate	0.1	lithium hydroxide monohydrate	0.4	24	96
Example 18	magnesium acetylacetonate	0.1	lithium hydroxide monohydrate	0.8	24	96
Example 19	magnesium acetylacetonate	0.1	lithium hydroxide monohydrate	2.0	24	96

[Examples 20∼31]

In each example, phenyl methacrylate was produced by carrying out the same procedure as in Example 1 except that magnesium acetylacetonate was replaced with the type and amount of magnesium compound (0.05 mol%∼0.5 mol%) specified in Table 3, and the amount of lithium hydroxide monohydrate specified in Table 3 was used (0.2 mol%∼2.0 mol%). The reaction result of each example obtained 5 hours or 24 hours after the start of reaction is shown in Table 3.

[Comparative Examples 11∼22]

Each comparative example was conducted to produce, or in an attempt to produce, phenyl methacrylate by carrying out the same procedure as in Examples 20∼31 except that lithium hydroxide monohydrate was not added. The reaction result of each comparative example obtained 5 hours or 24 hours after the start of reaction is shown in Table 3.

Table 3

	magnesium compound	added amount (mol%)	alkali metal compound	added amount (mol%)	reaction time (hr.)	yield of phenyl methacrylate (%)
Example 20	magnesium acetate tetrahydrate	0.05	lithium hydroxide monohydrate	0.2	24	93
Example 21	magnesium benzoate trihydrate	0.05	lithium hydroxide monohydrate	0.2	24	93
Example 22	magnesium methacrylate	0.05	lithium hydroxide monohydrate	0.2	24	93
Example 23	magnesium hydroxide	0.1	lithium hydroxide monohydrate	0.4	5	81
Example 24	magnesium chloride	0.1	lithium hydroxide monohydrate	0.4	5	84
Example 25	magnesium chloride hexahydrate	0.2	lithium hydroxide monohydrate	0.8	5	67
Example 26	magnesium bromide hexahydrate	0.2	lithium hydroxide monohydrate	0.8	5	85
Example 27	magnesium nitrate hexahydrate	0.2	lithium hydroxide monohydrate	0.8	5	82
Example 28	magnesium sulfate	0.2	lithium hydroxide monohydrate	0.8	24	92
Example 29	ammonium magnesium sulfate hexahydrate	0.2	lithium hydroxide monohydrate	0.8	24	46
Example 30	magnesium oxide	0.5	lithium hydroxide monohydrate	2.0	24	97
Example 31	magnesium carbonate hydroxide	0.5	lithium hydroxide monohydrate	2.0	24	96
Comp. Example 11	magnesium acetate tetrahydrate	0.05	-	-	24	88
Comp. Example 12	magnesium benzoate trihydrate	0.05	-	-	24	85
Comp. Example 13	magnesium methacrylate	0.05	-	-	24	88
Comp. Example 14	magnesium hydroxide	0.1	-	-	5	49
Comp. Example 15	magnesium chloride	0.1	-	-	5	0
Comp. Example 16	magnesium chloride hexahydrate	0.2	-	-	5	1
Comp. Example 17	magnesium bromide hexahydrate	0.2	-	-	5	1
Comp. Example 18	magnesium nitrate hexahydrate	0.2	-	-	5	5
Comp. Example 19	magnesium sulfate	0.2	-	-	24	0
Comp. Example 20	ammonium magnesium sulfate hexahydrate	0.2	-	-	24	0
Comp. Example 21	magnesium oxide	0.5	-	-	24	74
Comp. Example 22	magnesium carbonate hydroxide	0.5	-	-	24	64

[Example 32]

In a 100 mL capacity eggplant-shaped flask, 10.000 grams (106.26 mmol) of phenol, 7.657 grams (106.26 mmol) of acrylic acid, 23.664 grams (106.26 mmol) of di-t-butyl dicarbonate, 0.046 grams (0.53 mmol, 0.5 mol%) of lithium bromide, and 0.064 grams (0.53 mmol, 0.5 mol%) of magnesium sulfate were added successively. Then, reaction was carried out at 25°C while the mixture was stirred. Accordingly, phenyl acrylate was produced. The reaction result obtained 24 hours after the start of reaction is shown in Table 4.

[Examples 33~35]

Phenyl acrylate was produced in each of the examples by conducting the same procedure as in Example 32 except that lithium bromide was replaced with a type of alkali metal compound (0.5 mol%) specified in Table 4. The reaction result of each example obtained 24 hours after the start of reaction is shown in Table 4.

[Comparative Example 23]

The comparative example was conducted in an attempt to produce phenyl acrylate by the same procedure as in Example 32 except that lithium bromide was not added. The reaction result obtained 24 hours after the start of reaction is shown in Table 4.

[Comparative Example 24]

The comparative example was conducted in an attempt to produce phenyl acrylate by the same procedure as in Example 32 except that magnesium sulfate was not added. The reaction result obtained 24 hours after the start of reaction is shown in Table 4.

Table 4

	magnesium compound	added amount (mol%)	alkali metal compound	added amount (mol%)	reaction time (hr.)	yield of phenyl acrylate (%)
Example 32	magnesium sulfate	0.5	lithium bromide	0.5	24	48
Example 33	magnesium sulfate	0.5	lithium acetylacetonate	0.5	24	68
Example 34	magnesium sulfate	0.5	lithium carbonate	0.5	24	77
Example 35	magnesium sulfate	0.5	lithium hydroxide monohydrate	0.5	24	78
Comp. Example 23	magnesium sulfate	0.5	-	-	24	0
Comp. Example 24	-	-	lithium bromide	0.5	24	0

[Example 36]

In a 1L capacity eggplant-shaped flask, 153.370 grams (1629.69 mmol) of phenol, 140.300 grams (1629.69 mmol) of methacrylic acid, 362.938 grams (1629.69 mmol) of di-t-butyl dicarbonate, 0.027 grams (0.65 mmol, 0.04 mol%) of lithium hydroxide monohydrate, and 0.010 grams (0.16 mmol, 0.01 mol%) of magnesium hydroxide were added successively. Then reaction was carried out at 25°C while the mixture was stirred. Accordingly, phenyl methacrylate was produced. The reaction result obtained 48 hours after the start of reaction is shown in Table 5.

[Examples 37~62]

By using the material, catalyst and solvent shown in Tables 5~7 under the conditions specified in those tables and a smaller eggplant-shaped flask when applicable, corresponding carboxylic acid esters were produced by conducting the same procedure as in Example 36. The reaction results are shown in Tables 5~7.

Table 5

	carbolic acid (mol eq.)	added amount (mmol)	compound by formula (I) (mol eq.)	alcohol (mol eq.)	magnesium compound	added amount (mol%)	alkali metal compound	added amount (mol%)	solvent (mL)
Example 36	methacrylic acid (1.00)	1629.69	di-t-butyl dicarbonate (1.00)	phenol (1.00)	magnesium hydroxide	0.01	lithium hydroxide monohydrate	0.04	-
Example 37	methacrylic acid (1.00)	815.43	di-t-butyl dicarbonate (1.00)	2-phenylphenol (1.00)	magnesium hydroxide	0.02	lithium hydroxide monohydrate	0.2	-
Example 38	methacrylic acid (1.00)	326.40	di-t-butyl dicarbonate (1.00)	4-phenylphenol (1.00)	magnesium hydroxide	0.05	lithium hydroxide monohydrate	0.5	THF (215)
Example 39	methacrylic acid (1.00)	815.43	di-t-butyl dicarbonate (1.00)	1-naphthol (1.00)	magnesium hydroxide	0.02	lithium hydroxide monohydrate	0.2	-
Example 40	methacrylic acid (1.00)	326.40	di-t-butyl dicarbonate (1.00)	2-naphthol (1.00)	magnesium hydroxide	0.05	lithium hydroxide monohydrate	0.5	THF (110)
Example 41	methacrylic acid (1.00)	326.40	di-t-butyl dicarbonate (1.00)	2-naphthol (1.00)	magnesium hydroxide	0.05	lithium hydroxide monohydrate	0.5	THF (110)
Example 42	acrylic acid (1.00)	1800.02	di-t-butyl dicarbonate (1.00)	phenol (0.91)	magnesium hydroxide	0.01	lithium hydroxide monohydrate	0.04	-
Example 43	acrylic acid (1.00)	1800.02	di-t-butyl dicarbonate (1.00)	phenol (0.91)	magnesium hydroxide	0.01	lithium carbonate	0.05	-

INDUSTRIAL APPLICABILITY

The method for producing a carboxylic acid ester related to the present invention is capable of producing the carboxylic acid ester more efficiently and cost-effectively than in conventional methods. In addition, by using the method for producing a carboxylic acid ester related to the present invention, a carboxylic acid ester is obtained at high yield under mild reaction conditions. Furthermore, since various carboxylic acids and alcohols may be used as raw materials in the method for producing a carboxylic acid ester related to the present invention, the substrate generality is significantly broader than in conventional methods.

Claims

A method for producing a carboxylic acid ester, comprising:
a step for reacting a compound represented by formula (I) below, a carboxylic acid and an alcohol in the presence of at least one type of magnesium compound and at least one type of alkali metal compound
in formula (I), R¹ and R² each indicate a C1∼C20 hydrocarbon group,

wherein the amount of the magnesium compound is in a range of 0.001∼1000 mol% relative to the compound represented by formula (I),

wherein the amount of the alkali metal compound is in a range of 0.001∼1000 mol% relative to the compound represented by formula (I),

wherein the magnesium compound is a salt with inorganic acids such as magnesium oxide, magnesium hydroxide, magnesium carbonate, magnesium bicarbonate, magnesium silicate, magnesium sulfate, ammonium magnesium sulfate, magnesium nitrate, magnesium phosphate, magnesium hydrogen phosphate, ammonium magnesium phosphate, magnesium borate, a magnesium salt of halogen acids, a magnesium perhalogenate, and a magnesium salt of hydrohalic acids; a salt with organic acids such as magnesium carboxylate, magnesium peroxycarboxylate, and magnesium sulfonate; a complex salt such as magnesium acetylacetonate, magnesium hexafluoroacetylacetonate, magnesium porphyrin, magnesium phthalocyanine, and magnesium cyclopentadienyl, wherein these magnesium salts may be any hydrate or anhydride, and

wherein the alkali metal compound is a salt with inorganic acids such as alkali metal hydrides, oxides, hydroxides, carbonates, bicarbonates, sulfates, nitrates, phosphates, borates, a salt of halogen acids, perhalogenates, a salt of hydrohalic acids, and thiocyanates; a salt with organic acids such as alkali metal alkoxides, carboxylates, and sulfonates; a salt with organic bases such as alkali metal amides and sulfoamides; a complex salt such as alkali metal acetylacetonates, hexafluoroacetylacetonates, porphyrins, phthalocyanates, and cyclopentadienates, wherein these alkali metal salts may be any hydrate or anhydride.
The method for producing a carboxylic acid ester according to Claim 1, wherein the metal of the alkali metal compound is lithium.
The method for producing a carboxylic acid ester according to Claim 1 or 2, wherein the compound represented by the formula (I) is di-t-butyl dicarbonate.
The method for producing a carboxylic acid ester according to any of Claims 1∼3, wherein the carboxylic acid is a (meth)acrylic acid.
The method for producing a carboxylic acid ester according to any of Claims 1∼4, wherein the alcohol is an aromatic alcohol.
The method for producing a carboxylic acid ester according to any of Claims 1∼5, wherein reaction is carried out by adding 0.1∼10 mol of the carboxylic acid and 0.1∼10 mol of the alcohol relative to 1 mol of the compound represented by the formula (I).
The method for producing a carboxylic acid ester according to any of Claims 1∼6, wherein reaction is carried out in the presence of the magnesium compound and alkali metal compound, each being set at 0.001∼1000 mol% of the alcohol.